Neutral developing of azoic colors



United tts US. Cl. 8-45 12 Claims ABSTRACT OF THE DISCLOSURE A neutral developing composition and a process for employing the same, such composition comprising a coupling component, a diazo amino compound, a volatile oxygen-containing, water soluble nitrogenous organic base, and a sulfonated long chain alkyl carboxylic acid.

This invention relates to an improved process for neu tral developing of azoic colors and to the compositions used therein.

More specifically, this invention relates to an improved process for neutral developing of azoic colors wherein the dyeing or printing composition contains a sulfonated long chain carboxylic acid and a Water soluble nitrogeneous oxygen-containing organic base.

Prior art processes for developing azoic compositions may be broadly classified into acidic developing and neutral developing.

In acidic developing the diazo compound and the coupling component are dissolved in a caustic alkali solution. The solution is thereafter made into a suitable paste by the addition of a thickening agent such as starch or gum tragacanth. After the paste is applied to the textile. as by printing, the dye is developed by exposing the textile to acidic steam. The acidic steam operates to split the diazo moiety, and the thus freed diazo couples with the coupling component to produce the color. Generally, acetic acid is used as the acid component in the steam. While acidic developing produces the desired dyed effect, attendant therewith are .several disadvantages, primary of which is the offensive smell, irritating effect of the acid in the steam vapors, and corrosion of apparatus. Consequently, prior art workers have attempted to utilize a neutral steam developing process, thereby excluding the use of any acid.

Various processes for the neutral developing of azoic dyes have been utilized by prior art Workers. The basic approach has been the use of an alkaline base which, after printing, evaporates on exposure to neutral steam, thereby lowering the pH and enabling the diazo to split and couple with the coupling component and subsequently produce the color. These processes include the addition to the dye preparation of organic acids, phosphoric acid and salts of acids as shown in United States Patent No. 1,951,571; the use of amine salts and amides in the print composition as illustrated in United States Patent No. 2,008,966; the replacement of caustic alkali by a volatile amine, such as diethylamine, as taught by United States Patent No. 2,125,087; and the use of an oxygen containing Water-soluble nitrogeneous organic base, such as diethylaminoethanol, disclosed in United States Patent No. 2,232,405.

All of the neutral developing techniques described above suffer from several disadvantages. None of the methods, for example, are satisfactory for use with slow splitting diazo compounds, such as S-chloro-o-toluidine diazo stabilized with sarcosine, and S-chloro-o-anisidine diazo stabilized with sarcosine. Furthermore, the shades are duller than when the same dyestulf components are developed in acid steam. The duller shades are attributable primarily to slow coupling. The pH is usually higher in rent 3,436,168 Patented Apr. 1, 1969 neutral developing than in acidic developing and therefore dissociation of the diazoamino compound is slow, coupling is slow and decomposition of diazo is high.

While this method has been found advantageous when applied to neutral developing of azoic dyes, that is by developing the color by ageing in the presence of neutral steam, it has an added feature that it is also suitable for heat developing of azoic dyes, that is by subjecting the printed or dyed fabric to a temperature of 200-425 F. to develop color. It is especially useful in the Thermosol method wherein the printed or dyed fabric is dried and then subjected to a temperature of from about ZOO-450 F. for from about 15 seconds to 2 minutes.

It has been found in accordance with the present invention that, by using a printing or dyeing composition containing both a sulfonated long-chain carboxylic acid and an oxygen-containing water soluble nitrogenous organic base, the disadvantages of the prior art neutral developing processes may be overcome.

In those cases where the diazoamino cleaves with great difficulty it has been found advantageous to replace part of the sulfonated long-chain carboxylic acid with a strong organic acid.

Accordingly, it is an object of this invention to provide a novel neutral developing azo dye composition and process for using the same.

Another object of this invention is to provide a neutral developing azo dye composition and process which is remarkably effective in cleaving slow-splitting diazoamino compounds.

A further object of this invention is to provide a neutral developing azo dye composition and process wherein the colors developed are as consistently as bright as that produced in the conventional acidic developing composition and process.

Another object of this invention is to provide a neutral developing azo dye composition and process which can be employed with slow-splitting diazoamino compounds Which cannot be developed by the method described in United States Patent 2,232,405 which process is known as the RNA method.

Another object of this invention is to provide a composition and process wherein azoic compositions can be developed by a heat treatment.

These and other objects are accomplished by a composition containing a sulfonated long-chain carboxylic acid and a volatile water-soluble nitrogenous oxygen-containing organic base.

The volatile water-soluble nitrogenous oxygen-containing organic bases can be those recited in United States Patent No. 2,232,405, which patent is hereby incorporated by reference. Exemplary of the bases recited therein are ethylaminoethanol, diethylaminoethanol, N-propylaminoethanol, dimethylaminoethanol, dimethylaminobutanone, diethylaminoethanol methyl ether, N-hydroxyethylpyrrolidine, isobutylaminoethanol, isopropylaminoethanol. and dipropylam-inoethanol.

The sulfonated long-chain carboxylic acids are preferably the C to C sulfonated alkyl carboxylic acids such as oc-SlllfOltlllflC acid, u-sulfotridecoic acid, a-sulfomyristic acid, \oc-sulfopentadecanoic acid, a-sulfopalmitic acid, a-sulfomargaric acid, and a-sulfostearic acid. In addition to the ix-sulfonated carboxylic acids disclosed above, the term sulfonated long-chain alkyl carboxylic acids having from 12 to 18 carbon atoms is intended to include those compounds having one or more substituted sulfonated groups on any of the carbon atoms such as, for example, the p, 'y, 6, etc., position. The choice of acid and the position and number of sulfonated groups are dependent, for the most part, on prevailing economic considerations and the availability of the particular acid utilized.

The preferred method of carrying out this invention is to combine the oxygen-containing volatile amine and sulfonated alkyl carboxylic acid to produce a composition which in turn is combined with an alkaline solution which comprises approximately equal amounts of a stabilized diazoamino compound and an azoic coupler. This solution is usually thickened with starch tragacanth, Keltex gum, etherified starch or similar thickeners to printing consistency, printed on the fabric and subjected to neutral steam to develop color, or if desired subjected to dry heat to develop color.

As an alternative, the amine may be added to the azoic solution followed by addition of the sulfonated alkyl carboxylic acid under agitation.

Other additives may be included in the solution such as dispersants, solvents, urea, formaldehyde and the like.

The amount of the oxygen-containing amine and sulfonated alkylcarboxylic acid may vary. It has been found, for example, that .25 to 1.5 parts of oxygen-containing amine and .01 to .5 part of sulfonated alkylcarboxylic acid, to 1 part of color component provide satisfactory results.

In those cases where the diazoamino cleaves with great difiiculty it has been found that splitting is easier and faster if part of the sulfonated long chain carboxylic acid is replaced by a strong organic acid. The strong organic acid should have an ionization constant greater than about 1.8X10- In other words, the strong acid should be stronger than acetic acid. Such acids include monochloroacetic acid, glycollic acid, diglycollic acid, oxalic acid and the like. In using such acids, 5 to 50% of the sulfonated long-chain carboxylic acid is replaced in the formulations by the strong acid.

The parts indicated above and throughout the specifica tion and claims are parts by weight.

The following examples are intended to more specifically illustrate the invention, without being limitative in any manner.

Example I A developer composition of the following constituents was prepared:

Parts Diethylethanolamine 50 Diethylene glycol 23 a-SuIfostearic acid 20 Alipal LO-529 (sulfonated nonionic surfactant) 7 An azoic solution of the following constituents was prepared.

Parts Methyltaurine stabilized 5-chloro-oanisidine diazo 14.70 3-hydroxy-2-naphth-o-anisidine 14.50 Diethylene glycol 27.00 Caustic soda flake 2.50 adjusted to 100 parts with water.

A print paste was prepared as follows:

Grams Azoic solution 10 Urea Developer composition 10 Starch tragacanth 60 Three swatches of cotton cloth were printed with the above paste. One swatch was dried and aged for 5 minutes with neutral steam. The second swatch was dried and treated for 3 minutes at 300 F. The third swatch was dried and treated for 1 /2 minutes at 425 F. All three swatches developed a full bright red color. This demonstrates color development by neutral steaming, by usual heat development and by Thermosoling.

Example II Example I was repeated except that the azoic solution was replaced by a solution prepared by mixing the following components:

Parts Sarcosine stabilized S-chloro-o-toluidine diazo 12.20

3-hydroxy-2-naphth-o-phenetidide 15.40 Diethylene glycol 27.00 Caustic soda flake 2.50

adjusted to parts with water.

The three swatches were treated in the same manner as in Example I and each developed a full bright scarlet color.

Example III A print paste was prepared as in Example I except that the azoic solution consisted of the following ingredients:

Parts Sarcosine stabilized 5-chloro-o-toluidine diazo 11.5 Bis (acetoacet) dianisidide 9.0 Cellosolve 20.0 Caustic soda flake 1.8

adjusted to 100 parts with Water.

The three swatches were treated in the manner of Example I and each developed a bright yellow color.

Example IV An azoic solution of the following constituents was prepared:

Parts Sarcosine stabilized 5-chloro-o-toluidine diazo 15.5 3-hydroxy-2-naphth-o-toluidide 16.0 Diethylene glycol 27.0 Caustic soda flake 2.5

adjusted to 100 parts with water.

A printing paste was prepared which consisted of:

Parts Starch tragacanth 50.0 Urea 20.0 Developer prepared as in Example I 7.0 Azoic solution prepared above 10.0 Water Cotton was printed with this paste. When aged by neutral steam for 5 minutes and when subjected to heat at 300 F. for 3 minutes, bright red colors were obtained.

Example V Example VI Example I was repeated except that the azoic solution was replaced by a solution prepared by combining the following components:

Parts 2,5-dichloroaniline diazo stabilized with N-ethyl-S- sulfoanthranilic acid 16.0 3-hydroxy-2-naphth-o-phenetidide 10.0 Cellosolve 20.0 Caustic soda flake 2.1

t The three swatches were treated in the same manner as in Example I and each developed a bright orange color.

Example VII The following printing paste was formulated:

Parts Starch tragacanth 55.0 Urea 20.0 Developer prepared as in Example I 10.0

Azoic solution prepared as in Example VI 10.0

Dispersed dye prepared by coupling 3-hydroxy-2- naphth-o-toluidide with 2-chloro-6 trifiuoromethylaniline diazo 5.0

A 6535% Dacron-cotton fabric was printed with this paste, dried and subjected to a temperature of 400 F. for 1 /2 minutes. A solid orange union shade was produced.

Example VIII Example II was repeated except that the stabilized diazo was replaced by S-chloro-o-toluidine diazo stabilized with cyanamide.

The three swatches were treated in the same manner as in Example I and each developed a full bright scarlet color.

Example ]X The following print paste was formulated:

Parts O/W emulsion (commercial oil-in-water emulsion) 40.0 Polygun 260 (5%) (etherified starch) 15.0 Urea 20.0 Developer prepared in Example I 8.0 Azoic solution prepared in Example I 10.0 Water 7.0

Examples X XI XII Parts Parts Parts Polygun 260 (5%) 50 so 50 Urea 20 20 20 Developer of Example I 5 5 The azoic solution of Example 10 Azoic blue solution 10 Azoic black solution Water 10 10 10 The azoic blue solution consisted of:

Parts Methyltaurine stabilized dianisidine tetrazo 8.5 3-hydroxy-2-naphthanilide 11.0 Cellosolve 5.0 Diethylene glycol 10.0 Caustic soda flake 5.0

The azoic black solution consisted of:

Parts Methyltaurine stabilized dianisidine tetrazo 15.0 7 and S-amino-S-(phenylazo)-l-naphthylamine 4.8 3-hydroxy-2-naphthanilide 4.5 Diethylene glycol 10.0 Caustic soda flake 4.5

Cotton was printed with the paste of Example X, dried and subjected to a temperature of 400 F. for 1 minutes and also a second print was steamed in neutral steam for 3 minutes. In both cases a bright yellow coloration occurred.

Two swatches of cotton were printed with the paste of Example XI. When developed as described in Example X bright blue prints were obtained.

Two swatches of cotton were printed with the paste of Example XII. When developed as described in Example X deep black prints were obtained.

Example XIII The following composition was formulated:

Parts Urea 30.0 Alginate gum (1-100) 30.0 Water 50.0 Developer of Example I 15.0 Azoic solution of Example II 10.0

Dispersed dye from 5-chloro-o-toluidine diazotized and coupled with 3-hydroxy-Z-naphtho-o-toluidide 8.0

65-35% Dacron-cotton material was padded with this solution, dried and subjected to a temperature of 400 F. for 1 minutes. A bright solid union scarlet was obtained.

Example XIV The following composition was formulated:

Parts Urea 30.0 Alginate gum 1:100 30.0 Water 50.0 Developer of Example I 15.0 Azoic solution of Example I 10.0

Dispersed dye from 5-chloro-o-anisidine diazotized and coupled with 3-hydroxy-2-naphth-o-toluidide 4.0 Dispersed dye from 4-(o-tolyl-azo-o-toluidine diazotized and coupled with 3-hydroxy-2-naphth-ophenetidide 4.0

A 65-35% Dacron-cotton swatch was padded with this solution, dried and subjected to a temperature of 400 F. for 1 /2 minutes. A deep bluish red union color was obtained.

Example XV In order to demonstrate the effectiveness of the developer of the instant invention, the azoic dye solutions utilized in Examples I thru IV were prepared in a conventional paste formulation and both neutral and acid developed.

The paste compositions were as follows:

Grams Stabilized dye solution 10.0 Starch tragacanth 60.0 30% caustic soda solution 1.0 Water 29.0

Four swatches of cotton cloth were printed with the above compositions. For each swatch, the paste composition was varied by using the azoic solutions of Examples I thru IV. After ageing in neutral steam for 5 minutes, it was observed that very little color developed.

However, when four identicall printed swatches of cloth were exposed to acid steam for 5 minutes, a bright full color developed, commensurate with that produced when Examples I thru IV were developed in neutral steam.

This comparison clearly demonstrates the remarkable effectiveness of the developer composition of the instant invention in developing slow developing azoic dye solutions by a neutral developing technique.

Example XVI A developer composition was compounded as follows:

Grams Diethylethanolamine 35 a-sulfopalmitic acid 20 The following print pastes were made up employing the above developer composition.

Grams Azoie solution of Example I III.

IV Alginatc gum (5%) Urea- Developer composition Three swatches of cotton cloth were printed with each of the four pastes. One set was dried and aged 5 minutes in neutral steam, one set was dried and heated to 300 F. for 3 minutes, the third set was dried and heated to 425 F. for 1 /2 minutes. In each case, full bright color developed.

Example XVII Example XVI was repeated except that the developer composition of the following composition was utilized:

Emulphor ELA (polyoxylated vegetable oil, General Aniline and Film Corp.) 7.0 u-Sulfostearic acid 13.0 Glycollic acid 7.0

A print paste was made in the manner of Example I except that the developer solution of Example I was replaced by this solution.

Three swatches of cloth were treated as in Example I. The color produced was commensurate with that produced in Example I; however the color developed quicker.

What is claimed is:

1. A dye composition comprising coupling components, diazoamino compounds, volatile oxygen-containing, watersoluble nitrogeneous organic bases and sulfonated longchain alkyl carboxylic acids.

2. A composition according to claim 1, wherein the sulfonated long-chain alkyl carboxylic acid has from 12 to 18 carbon atoms.

3. A composition according to claim 1, wherein the sulfonated long-chain alkyl carboxylic acid is a-sulfolauric acid.

4. A composition according to claim 1, wherein the sulfonated long-chain alkyl carboxylic acid is a-sulfopalmitic acid.

5. A composition according to claim 1, wherein the s-ulfonated long-chain alkyl carboxylic acid is a-sulfostearic acid.

6. In the method of neutral steam developing of azoic dyes, the improvement which comprises applying to the material to be dyed a developer composition comprising coupling components, diazoamino compounds, volatile nitrogeneous oxygen-containing organic bases, and sulfonated long-chain alkyl carboxylic acid.

7. The method according to claim 6, wherein the suitenated long-chain alkyl carboxylic acid has from 12 to 18 carbon atoms.

8. The method according to claim 6, wherein the sulfonated long-chain alkyl carboxylic acid is a-sulfolauric acid.

9. The method according to claim 6, wherein the sulfonated long-chain alkyl carboxylic acid is a-sulfopalmitic acid.

10. The method according to claim 6, wherein the sulfonated long-chain alkyl carboxylic acid is a-sulfostearic acid.

11. A composition according to claim 1 wherein 5 to 50% by weight of the sulfonated long-chain alkyl carboxylic acid is replaced by a strong organic acid having an ionization constant of at least 1.80Xl0 12. A method according to claim 6 wherein 5 to 50% by weight of the sulfonated long-chain alkyl carboxylic acid is replaced by a strong organic acid having an ionization constant of at least 1.80 10- References Cited UNITED STATES PATENTS 2,232,405 2/ 1941 Schmelzer 845 NORMAN G. TORCHIN, Primary Examiner.

T. J. HERBERT, JR., Assistant Examiner.

US. Cl. X.R. 846 

